Propellants and refrigerants based on trifluoropropene

ABSTRACT

Aerosol propellants and refrigerants based on trifluoropropene (CF3CH CH2) are disclosed.

United States Patent 1 Butler 51 Mar. 27, 1973 PROPELLANTS AND REFRIGERANTS BASED ON TRIFLUOROPROPENE Inventor: Anthony J. Butler, Greensboro,

Assignee: Dow Corning Corporation, Midland,

Mich.

Filed: Nov. 26, 1971 Appl. No.: 202,656

Related U.S. Application Data Division of Ser. No. 8l,l23, Oct. 15, 1970.

U.S. Cl ..252/67, 252/305 Int. Cl. ..C09k 3/06 Field 0i Search ...252/6769;

Primary Examiner-Mayer Weinblatt Assistant Examiner-Harris A. Pitlick Attorney-Robert F. Fleming, Jr. et a].

[ M ABSTRACT Aerosol propellants and refrigerants based on trifluoropropene (CF,CH=CH are disclosed.

4 Claims, No Drawings PROPELLANTS AND REFRIIGERANTS BASED ON TRHFILUOROPROPENE This application is a division of application Ser. No. 81,123 filed Oct. 15, 1970.

This invention relates to an aerosol product which includes a propellant wherein the improvement comprises employing trifluoropropene as l to 100 percent by weight of the propellant.

This invention also relates to a refrigeration system in which the refrigerant undergoes a change from the liquid to the vapor state wherein the improvement comprises employing trifluoropropene as 1 to 100 percent by weight of the refrigerant.

With the ever increasing number of aerosol products being marketed there is an increasing demand for new propellants to solve the problems encountered in dispensing the materials and to meet the needs involved with specific products and uses.

Similarly, with improvements in existing refrigeration systems, and the designing of new refrigeration systems, there is an increasing demand for new refrigerants which will function satisfactorily.

Most aerosol products contain three major components. These are the active ingredient, the solvent and the propellant. While these components have been referred to in the singular, it is believed obvious that each component can consist of more than one ingredient. One aspect of the present invention is directed to the propellant used in aerosol products. It has been found that trifluoropropene can be employed as 1 to 100 percent by weight of the propellant. That is, trifluoropropene can be used alone as the propellant in an aerosol or it can be used in combination with other propellants in an aerosol. it should be noted at this point that while the function of the trifluoropropene is basically and primarily that of a propellant that it may also perform an incidental function as a solvent and this is within the scope of the term propellant as used in this specification and claims.

The propellant provides the pressure that forces the aerosol product from the container when the valve is opened. Also, the propellant has an influence on whether the product is discharged in the form of a spray, stream, or as a foam. Variations in the propellant can also influence, for example, whether one obtains a course or fine spray or whether one obtains a good or poor foam. Thus it can be seen that the discovery that trifluoropropene can be employed as a propellant gives the aerosol manufacturer greater latitude in preparing products than heretofore available to him.

As noted above, trifluoropropene can be used as the sole propellant or in combination with other known propellants. Examples of suitable propellants which can be employed in combination with trifluoropropene include fluorodichloromethane, difluorochloromethane, fluorotrichloromethane, difluorodichloromethane, 1,2,2-trifluoro-l ,1 ,2- trichloroethane, 1,1 ,2,2-tetrafluoro-1 ,2- dichloroethane, 1,1 ,2,2,2-pentafluorol -chloroethane, 1 ,1-difluoro-l-chloroethane, 1,1-difluoroethane, octafluorocyclobutane, methylene chloride 1,1,1- trichloroethane, tetrafluoroethylene, vinyl chloride, propane, n-butane, isobutane, ethylene, dimethyl ether, nitrogen, nitrous oxide, carbon dioxide and mixtures thereof. It will be noted from the examples given that the trifluoropropene can be employed in combination not only with other liquified gas propellants but also in combination with compressed gas propellants. No meaningful limitations can be set as to the relative proportions of the individual propellants to be used in combination as this depends on the individual needs and the particular product being formulated.

Another aspect of this invention is the use of trifluoropropene as a refrigerant. The most common refrigeration systems today are designed to carry out a process for producing cold in which a working substance called the refrigerant is caused to undergo a physical change. The most widely used physical change is that in which the refrigerant undergoes a change from the liquid to the vapor state.

Trifluoropropene can be used as the sole refrigerant in a system or it can be used in combination with other refrigerants. By way of illustration, trifluoropropene can be used in admixture with fluorodichloromethane, difluorochloromethane, fluorotrichloromethane, difluorodichloromethane, 1,2,2-trifluoro-l ,i ,2- trichloroethane, 1,1 ,2,2-tetrafluoro-l ,2- dichloroethane, l,l,2,2,2-pentafluoro-1-chloroethane, l, 1 -difluoro- 1 -chloroethane, 1,1-difluoroethane, octafluorocyclobutane, methylene chloride, 1,1,1- trichloroethane, tetrafluoroethylene, vinyl chloride, propane, n-butane, isobutane, ethylene, dimethyl ether, nitrogen, nitrous oxide, carbon dioxide and mixtures thereof. No meaningful limitations can be set as to the proportions to be used as the choice of a refrigerant for a specific application is determined by the thermodynamic properties, physical properties and chemical properties needed for that application.

Now in order that those skilled in the art may better understand how the present invention can be practiced, the following examples are given by way of illustration and not by way of limitation. Trifluoropropene has a boiling point of about --22C. and a vapor pressure of approximately 60 pounds per square inch gauge (psig) at 25C. Trifluoropropene is flammable, and acute studies indicate it to be relatively nontoxic. Ali percents referred to herein are by weight unless otherwise specified.

EXAMPLE 1 Percent Vapor Pressure Trifluoropropene 1.1,1-trichloroethane (psig) I0 90 2O 20 80 3 1 30 4-1 40 60 49 50 5O 54 60 40 60 70 30 6'? 20 7 i 10 82 EXAMPLE 2 Six units of three different aerosol products were packaged using trifluoropropene as the propellant. Two control units were prepared for purpose of comparison with each set and were identical in every respect except that difluorodichloromethane was used as the propellant. The aerosol products were a release agent for cooking utensils (Pan Shield), a water repellent agent for leather goods (Shoe Saver), and a textile treating agent (Fabriglide). Three units and one control of each set were stored at room temperature and three units and one control were stored at 100F. The first samples (one from room temperature and one from 100F.) were opened and examined after two weeks, the second samples were checked a month later, and the final samples with controls a month after that. After 2% months of shelf-life all products where stable with no deviations from the control units. There was no change in the product color nor any attack on the aerosol container. Pressures remained relatively constant, and weight losses were negligible. It was noted that the trifluoropropene had a light characteristic odor which could be masked with perfume if found objectionable.

Although the vapor pressure of trifluoropropene is lower than that of difluorodichloromethane, in combination with such materials as l,l,1-trichloroethane, currently available data indicates that it gives a slightly higher difluorodichloromethane that data indicates that it is possible to use less trifluoropropene than difluorodichloromethane in an aerosol product to attain the desired pressure.

than that of combinations.

similar Therefore,

pressure EXAMPLES When the following propellants are substituted for trifluoropropene in the aerosol products of Example 2, similar results are obtained:

9% propane EXAMPLE 4 When the following refrigerants are used in a refrigeration system in which the refrigerant undergoes a change from the liquid to the vapor state, such as the refrigeration systems found in refrigerators and freezers, ogpod cooling is obtained:

A. l trifluoropropene B. trifluoropropene 10% difluorodichloromethane 80% trifluoropropene 20% l,2,2-trifluoro-1,l,2-trichloroethane 50% trifluoropropene 50% fluorotrichloromethane E. 45% trifluoropropene 45% fluorotrichloromethane 10% isobutane 1% trifluoropropene 99% fluorotrichloromethane That which is claimed is:

1. In a refrigeration process in which the refrigerant undergoes a change from the liquid to the vapor state, the improvement comprising employing trifluoropropene as 1 to 100 percent by weight of the refrigerant, the balance of the refrigerant being selected from the group consisting of fluorodichloromethane, difluorochloromethane, fluorotrichloromethane, difluorodichloromethane, 1,2,2-trifluoro-l ,l ,2-trichloroethane, 1,1 ,2,2 tetrafluoro-l ,2-dichloroethane, 1,1 ,2,2,2-pentafluorol-chloroethane, 1,1-difluoro-1-chloroethane, 1,1- difluoroethane, octafluorocyclobutane, methylene chloride, 1,1,1-trichloroethane, tetrafluoroethylene, vinyl chloride, propane, n-butane, isobutane, ethylene, dimethyl ether, nitrogen, nitrous oxide, carbon dioxide and mixtures thereof.

2. A refrigeration process as defined in claim 1 wherein the trifluoropropene constitutes 100 percent of the refrigerant.

3. A refrigeration process as defined in claim 1 wherein the trifluoropropene constitutes less than 100 percent of the refrigerant.

4. a composition consisting essentially of from 1 to 91 percent by weight of trifluoropropene, the balance of the composition being selected from the group consisting of fluorodichloromethane, difluorochloromethane, fluorotrichloromethane, difluorodichloromethane, 1,2,2- trifluoro-1,1,2- trichloroethane, 1,1 ,2,2-tetrafluorol ,2- dichloroethane, 1,1 ,2,2,2-pentafluoro-l-chloroethane, l, l -difluoro-l -chloroethane, 1,1-difluoroethane, octafluorocyclobutane, methylene chloride, 1,1,1- trichloroethane, tetrafluoroethylene, vinyl chloride, propane, n-butane, isobutane, ethylene, dimethyl ether, nitrogen, nitrous oxide, carbon dioxide and mixtures thereof. 

2. A refrigeration process as defined in claim 1 wherein the trifluoropropene constitutes 100 percent of the refrigerant.
 3. A refrigeration process as defined in claim 1 wherein the trifluoropropene constitutes less than 100 percent of the refrigerant.
 4. a composition consisting essentially of from 1 to 91 percent by weight of trifluoropropene, the balance of the composition being selected from the group consisting of fluorodichloromethane, difluorochloromethane, fluorotrichloromethane, difluorodichloromethane, 1,2,2-trifluoro-1,1,2-trichloroethane, 1,1,2,2-tetrafluoro-1,2-dichloroethane, 1,1,2,2,2-pentafluoro-1-chloroethane, 1,1-difluoro-1-chloroethane, 1,1-difluoroethane, octafluorocyclobutane, methylene chloride, 1,1,1-trichloroethane, tetrafluoroethylene, vinyl chloride, propane, n-butane, isobutane, ethylene, dimethyl ether, nitrogen, nitrous oxide, carbon dioxide and mixtures thereof. 